CN1040148A - The method of annihilating toxical waste and plasma chemical reactor - Google Patents
The method of annihilating toxical waste and plasma chemical reactor Download PDFInfo
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- CN1040148A CN1040148A CN89105527.4A CN89105527A CN1040148A CN 1040148 A CN1040148 A CN 1040148A CN 89105527 A CN89105527 A CN 89105527A CN 1040148 A CN1040148 A CN 1040148A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/085—High-temperature heating means, e.g. plasma, for partly melting the waste
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2204/00—Supplementary heating arrangements
- F23G2204/20—Supplementary heating arrangements using electric energy
- F23G2204/201—Plasma
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/14—Gaseous waste or fumes
- F23G2209/142—Halogen gases, e.g. silane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
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Abstract
Toxic waste is blended in the steam plasma beam, halogen atom in the halogenic hydrocarbon transforms in the plasma reaction level, hydrocarbon then is gasificated into stable combustible, in the oxide isolation of order of reaction again, cool off, and combustible burnt into carbon dioxide and water, they are discharged in the air after alkali cleaning.Plasma reaction is to carry out in an earthenware that is installed with (7) unstressedly, and pipe (7) outside is with medium cooling, this cooling medium in order of reaction again as oxidant.Temperature in the pipe (7) should be coordinated for avoiding harmful substance to be passed.The present invention is particularly useful for destroying FCKW.
Description
The present invention is used to destroy solid-state, gaseous state, liquid state or ointment shape noxious material with any stable components or the refuse that contains Toxic matter, the waste material of especially chloride, fluorine compounds, and they result from chemical industry, microelectronics industry and other industrial department.
In current all industrialized countries in the world, all produce a large amount of waste materials in chemical change, chemical mineral processing and chemical synthesis process, a part contains direct destruction physiological potency or extremely toxic substance carcinogenic and those suspection destruction fecundities.Belong to the fat of for example high chlorine of this class material or many chlorine (high fluorine or polyfluoro) or aromatic substance, diox (Dioxine), furans (Furane), also also have inorganic compound, as fluoride, boride, Polychlorinated biphenyls etc.This class material generally all has good chemistry and heat endurance except harmfulness and toxicity are arranged, their concentration major parts in refuse all smaller (ppm scope) can not be avoided its danger to such concentration, and the possibility of reprocessing is very little.A plurality of (until hundreds of) poisonous kind might be arranged in addition in a kind of refuse and deposit.The production residue that this class refuse produces when being typically circuit board dry etching in the production residue of chemical industry or pharmaceuticals industry and the microelectronics industry.
For above-mentioned reasons, the whole world has only two kinds of pollutant processing methods: direct storing method and high-temperature combustion method.
In first method, refuse is not eliminated usually, change a lot of money they are preserved, and take special safety measure, with prevention atmosphere pollution and underground water, also must be continuously in addition supervisory to this, although so, Bi Jing still means and has a kind of eternal dangerous matter sources.
High-temperature combustion method (for example using rotary furnace) is operated in 1000 ℃ scope, and it has following shortcoming:
1. the temperature that can reach is not enough to eliminate whole harmful substances usually, only reduces its quantity in principle.
2. the best harmful substance (as many chlorine aromatic substance) of heat endurance is placed in the atmosphere, because exist the uneven temperature field in the burning level of each combustion process, thereby constantly harmful substance is sent into chimney from colder zone, and thereby enters atmosphere.
3. some zone in the burner hearth of hundreds of degrees centigrade of scopes can additionally generate diox and furans.This situation is the basic reason of the confirmed diox of the special-purpose burner generation of rubbish just.
4. this method can't be destroyed incombustible refuse.Harmful substance flashes to gas phase from refuse, and thereby incites somebody to action the Toxic that will not be transformed and put into atmosphere.
Another shortcoming of rotary furnace system is that uncontrollable gas pollutes the part of stove inside by the hole of stove import and export.
More than two kinds of methods (storing and high-temp combustion) all be not suitable for the harmful substance of destroying in the gaseous state waste material.
For this class waste material, when for example making microprocessor in the waste discharge district of dry etching operation poisonous fume, use absorption process or absorption method, therefore succeed in doing and from waste gas, remove noxious material at least in part, thereby alleviate the burden (seeing JP-PS 58122025, JP-PS 62030525, JP-PS 62136230, JP-PS 59109227, JP-PS 60044025) of atmosphere.
The major defect of these methods is not eliminate poisonous substance, but has formed the contaminated solid-state or stripping liquid with identical or higher concentration of narmful substance again, can only store them to get up in the storehouse, thereby bring above-mentioned known whole shortcomings.
Also known have plasma pyrolysis and plasma firing method to destroy harmful substance.The arc-plasma firing method uses air plasma to carry out work.For liquid and solid waste are equipped with revolution or plasma reactor, so that the electric arc rotation.Electric arc acts directly on the refuse in the swinging plasma reactor.This method cost is high and be subject to interference, exists the danger that harmful substance is overflowed from moving parts.Having very big temperature difference between arc region and all the other districts of reactor is another shortcoming of the method, therefore exists harmful substance all the time by the danger of reactor than the cold-zone.
Use air to also have the shortcoming of some essence as plasma gas:
1. under the required hot conditions of work, especially produce carbon monoxide in the arc plasma tagma, it is the additional harmful substance that produces.
2. when using air as plasma gas, it only is 1 that the chemical reaction ability and the ratio of chemically inert plasma composition are arranged: 4(20% oxygen, 80% nitrogen).This is because the nitrogen of the main component in the air of using, even under condition of plasma, also form the chemical reaction class hardly, only just resolve into the chemical reaction atom being higher than 5000k, and, can not surpass 3500k in the temperature of the method ionic medium body in fact because energy.So all nitrogen only plays thermodynamic (al) effect.Directly draw another shortcoming thus, promptly owing in the workspace of equipment, existing undecomposed nitrogen, so the energy density that reaches is much smaller.
3. the method especially is not suitable for the hydrocarbon that transforms high chlorine low hydrogen or high fluorine low hydrogen, for example in the waste gas of microelectronics industry, contained like that, because a large amount of chlorine and fluorine discharge the form that becomes molecule from product can not be decomposed (for example becoming HCL) with hydrogen.
4. lack the hydrogen that is used for the atom transfer reaction for the needed state of atom of Toxic of decomposition texture complexity.
This plasma firing method produces mechanical wear, sealing problem and needs bigger space owing to the part (swinging plasma reactor) that the mechanical movement done is arranged, thereby can not satisfy the white area and the middle high-purity requirement of gray area (Wei β-und Grauzonen) of microelectronics industry.
Introduced the scheme of another kind of annihilating toxical waste in DD-PS 245941, it is by means of H
2Plasma liquid towards and off-gas are implemented plasma high-temperature and are decomposed.This method has following technical shortcoming:
1. particularly to stable many chlorine aromatic substance, its chemical corrosion is not enough for hydrogen plasma.
2. acutely reduced atmospheric pressure given in advance because of hydrogen plasma, this produces injurious effects for the purpose that this method will reach, though because might carry out atom transfer reaction in principle, to decompose steady (randstaendig) H of refuse intermediary and Cl atom continuously and they are at H
2Or the stable keys among the HCl, but can not destroy carbon skeleton constantly, that is to say that the macromolecular structure of stable harmful substance remains unchanged.
3. the method needs a quenching level, therefore in hydrogen plasma, has promoted from undecomposed hydrocarbon structure, uncontrolledly generates the new harmful substance that has changed chemical constitution.But this method can not guarantee to stablize (harmless) with toxic waste in carbonization close.
4. the plasma pyrolysis level has acutely reduced atmospheric pressure, causes generating from input debirs carbon black (pyrolysis coke).Cause following shortcoming thus:
4.1 be necessary to clear up each course of work level every certain hour, the carbon black of these accumulations can be polluted, thereby threatens the equipment operator.
4.2 the main carbon black that in the plasma pyrolysis level, generates, after by this method quenching, have in the burning level of air or oxygen and run into difficulty, because foreign peoples's carbon black is difficult to carry out completing combustion in fluid reactor, contaminated carbon black pellet has the danger in following stages scurried into and the atmosphere.
4.3 for avoiding generating the explosive mixture, the plasma pyrolysis level must be all the time worked under the condition of superpressure slightly.This just is certain to that carbon black is entered in the surrounding environment, and this will be for clean clear district the bringing on a disaster property consequence of for example circuit board factory.
5. the pyrolytic reaction of carrying out owing to the plasma pyrolysis level has endothermic character, thereby causes along the axial cooling of plasma beam.The result who causes thus makes follow-up burning level work temperature lower.Because in the plasma pyrolysis level, chlorine has generated the hydrocarbon of new chlorine, and it has high stability, therefore finally can not guarantee to eliminate them.
6. the method is not suitable for the inorganic constituents (for example silicon, vanadium, boron compound) that transforms in the refuse, because in plasma pyrolysis level or quenching level, they can produce poisonous metallo-organic compound (BH for example
3).
7. according to said method, the burning level that is located at the back will be finished the task of a difficulty, its multiple indefinite compound that must burn simultaneously.
DE-OS 3427710 has introduced a kind of equipment that directly carries out the plasma pyrolysis refuse in electric arc.The method scope of application is similar to the DD-WP 245941 that had introduced the front.
The method of known in addition destruction (burning) household garbage (DE-OS 3605785, DE-OS 3524316, DE-OS 3424710).
Because destroying the high stability noxious material has any problem technically, so refuse that this class forms in chemical industry, microelectronics industry and other industrial department, at present, sub-fraction is imperfect combustion in having the conventional high-temperature combustion equipment of above-mentioned shortcoming, and major part is sent to special-purpose rubbish warehouse and does nonvolatil storage.
Because the dangerous garbage of whole world storage is more and more, thus the difficulty also increasing (especially in the area that is densely populated) of seeking and opening up suitable storage place, so they more and more widely the ground warp water and air leak in the surrounding environment and go.
Big in the plasma chemical reactor owing to making it thermic load by plasma, so always be provided with and the irrelevant device that can give strong water-cooled of the course of work of being carried out.Only in this way could adopt steel or high-temperature steel, copper or brass etc. to make reactor material, plasma chemistry process and surrounding environment are kept apart.To the cooling of this necessity of reactor, make between the core of plasma beam and the reactor wall and form a strong radial symmetry gradient.The shortcoming of bringing therefrom is, it is very low to spray into the intrafascicular that part of feed stock conversion that is near wall region of plasma.In some plasma chemical method (for example pyrolytic of natural gas), this not necessarily can bring the shortcoming of essence, because can participate in circulation again in the Returning reactor at the unconverted natural gas of reactor near wall region, but the cooling of requisite wall is to reduce the thermal efficiency and conversion ratio more or less eventually.Also known other structure of reactor form is provided with the mosaic coating made from the good material of heat endurance and chemical stability (for example pyrolysismethod make graphite) in the reactor.Do like this and can significantly improve efficient; but the problem of bringing is must carry out mechanical connection between mosaic coating and reactor material; and they have different thermal expansions; therefore when being heated to high temperature, produce mechanical stress; or because starting and shutdown cause alternate stress, thereby make inlaid material fatigue and reactor is damaged.Also known a series of H that utilizes
2Or air plasma burns the plasma chemical method (DE-OS 3424710, DD-WP 245941, DE-DS 3605785, DD-WP 158128) of annihilating toxical waste by plasma pyrolysis or plasma, yet their structure of reactor fails to avoid the shortcoming that exists in the known structure.It is that electric arc is acted directly on the material that will be transformed that a kind of working method of known plasma firing method is arranged, and at this moment, owing between inside and outside the arc region very big thermograde is arranged, therefore can not accomplish to transform equably.Consequence of bringing and shortcoming are to use second plasma reactor to react again.
All exist the shortcoming that harmful substance may be passed from the cold-zone of nearly wall in the known structure of reactor form, and thereby the process level or the surrounding environment of contaminate subsequent.Want to reach the high malicious rate of removing, must stand some shortcoming sometimes, each is connected in series with plasma reactor to be about to two plasmatrons, so, except equipment cost and energy consumption increase,, in fact do not get rid of fully though the danger that harmful substance is passed has reduced.In addition, in known structure of reactor form, also exist the problem of control thermal stress and anti-alternating temperature-changing.
The objective of the invention is the whole noxious materials that to contain in the hazardous waste, for example diox, furans, Polychlorinated biphenyls, high chlorine or many chlorine (high fluorine or polyfluoro) fat or aromatic substance, silicon chloride, silicon fluoride, silicon or metallo-organic compound, boride etc., totally and unlimitedly utterly destroy, and be converted into harmless and help the product of surrounding environment.Need a reactor, it only in a plasma chemistry level, under the condition with high temperature stability and alternating temperature-changing stability, guarantees that 100% ground transforms the material that drops into, thereby avoids harmful substance to pass from the reactor cold-zone for this reason.
The present invention adopts a kind of method to achieve the above object, and this method is with the toxic waste of liquid, solid-state, ointment shape or gaseous state, and it is intrafascicular directly to send into water vapor plasma.The time of staying in a back to back plasma reaction level is 10
-3Second or longer.With order of reaction again that the plasma reaction level links to each other in, 10
-2Second or long interior article on plasma body bundle of time apply a kind of influence of oxide isolation.At this moment considering under the situation of residual enthalpy that temperature is up to 1500 ℃.Then resulting product gas is carried out alkali cleaning.The oxide isolation that quenching is used can be air or the another kind of mist that contains free oxygen.In a kind of satisfactory alkali cleaning equipment, product gas is used alkali lye prewashing in the pre-absorption device, and is cooled to be lower than 100 ℃ temperature, then cleans in a packed column again, at this moment is cooled to environment temperature.It is intrafascicular that gaseous state, liquid state and ointment shape refuse can directly be sent into water vapor plasma, and solid waste should be worn into the granularity less than 300 microns earlier, relends to help carrier gas to send into water vapor plasma intrafascicular.
A plasma chemical reactor of the present invention is applicable to enforcement the method, and it is connected with plasmatron by a flange.
The radial passage is arranged, in order to toxic waste or other material are sprayed in the plasma beam passage at the center of being located in the flange.In plasma reactor, a cone expansion ring is connected with flange, and the tensioner ring inner chamber is a mixing chamber.A pipe made from exotic material is placed on the tensioner ring loosely, and the inner chamber of pipe is the plasma reaction level.Concentric but the cylinder blanket of reactor is housed separated by a distancely with pipe.Spacing pin with respect to pipe is housed on the shell, it can guarantee to manage and shell between keep symmetry the annular gap.Shell is equipped with inlet branch towards the bottom of plasmatron.The length of shell is shorter than pipe, so pipe stretches in the order of reaction again.Order of reaction is made of bilayer sleeve again, and its internal diameter is identical with internal diameter of outer cover, and both connect by flange.Bilayer sleeve has constituted an annular gap formula cooling-water duct, and the cooling agent inlet branch is housed on it.
Can another diameter be installed with one heart less than its length in high-temperature resistant tube again, have only its half high-temperature resistant tube at most, it is rigidly secured on the cone expansion ring.
The working method of the inventive method is based upon on the following basis, be that water vapor plasma is in chemistry balance state, this poised state is corresponding to its average material temperature, it is characterized by most original hydrone and be decomposed into special reactive group, for example hydrogen atom or ion and electron gas composition.Temperature requirement is not less than 1500 ℃, because the hydrocarbon (for example hexachloro-benzene) of chlorine or fluorine especially, they are still stable until about 1300 ℃.
Water vapor plasma mixes the back they is applied heat and chemical affect with harmful substance, this just impels cause the fast reaction with high conversion between two kinds of compositions.Be characterized in priority or applying three kinds of influences on the noxious material of sending into simultaneously: at first make under the bigger effects of poisonous substance molecule of great majority, that is under the bombardment of water vapor plasma high energy structure, resolve into less fragment in heat.Next important step is, by having the reactive hydrogen atom of extensive chemical, peel off be situated between steady chlorine or fluorine atom from the basic skeleton of hydrocarbon (Grundger ü st), generate HCl or HF, they are more stable compounds under current condition, can make them finally stable through supercooling later on.The 3rd step of the water vapor plasma mechanism of action is to make remaining the dechlorination or the hydrocarbon skeleton of defluorination, especially through oxygen containing base HO for example
2, OH, O or O
2Chemical action, transform into stable Compound C O and H
2, carbon and hydrogen finally and completely stably are fixed up in these compounds, can not be reduced into macromolecular compound.A key character of the present invention is, utilizes hydrogen atom and oxygen base in the discharge water vapor plasma abreast, can finish two tasks simultaneously: the dechlorination of hydrocarbon skeleton or the defluorination of the steady halogen atom that is situated between; Corresponding (fixierende) gasification of hydrocarbon.
Sometimes silicon that in elementary product, contains or boride (BH for example
3) or metallo-organic compound, owing to existing oxide to make their oxidations, and thereby can be converted into nontoxic compound equally.The sulphur that might be present in the refuse can be converted into H
2S or SO
2The needed reaction time of illustrated process is at least 10
-8Second, the enthalpy of the water vapor plasma that this depends on before sending into harmful substance to be provided and the amount of noxious material.After the most appropriate reaction time of determining according to refuse kind and feature and selected plasma enthalpy, at that time may be by HCl, HF, CO, H
2, H
2S, SO
2, metal or half-metal oxide be (as SiO
2, B
2O
5Deng) and the inert fraction that in elementary product, contains sometimes (as N
2) oxide isolation (for example air) cooling that and then sprayed into of the plasma beam formed, the base that also exists chemical combination more at this moment, the plasma beam temperature descends (reducing to 1500 ℃ at most), makes plasma change common gaseous state into.Meanwhile, in order to make full use of the residual enthalpy in the gas, make stable combustible (CO, the H that exists in the gas
2, H
2S) carry out completely and with clearly defined objective oxidation with the oxygen in the gas with quenching.Through after this operation, comprise HCl, HF, CO in the product gas
2, steam, may also have SO
2With metal, half-metal oxide or element and also have N sometimes
2HCl, HF, SO
2, a part of CO
2In the two-stage alkali cleaning equipment of postposition, from product gas, removed, and by CO
2, steam and also have N sometimes
2The complete harmless mist of forming then enters in the surrounding environment and goes.Basically can reach 100% the malicious rate of removing by method of the present invention.Can destroy gaseous state, liquid or ointment shape refuse in the same way, or also can be the solid-state harmful substance of wearing into fine granularity.
The working method of plasma reactor can be illustrated by a technical example: conventional water-cooled plasma reactor has a violent radial symmetry gradient, it can make Toxic pass from colder near wall region, but by the plasma reaction level of plasma chemical reactor of the present invention, the air cooling that it enters by the inlet branch through reactor lower part.Therefore can improve the mean temperature (for example bringing up to 2500 ℃) of plasma reaction level, core temperature on the plasma slab axis is about 3000 ℃, this moment, the wall temperature of high-temperature resistant tube inboard rose to 2000 ℃, and this temperature guarantees to decompose all steady halogen atoms that are situated between reliably.So can not make harmful substance pass the primary plasma reaction zone again, the Toxic in the input refuse will change into CO, H fully
2And HCl.The plasma of the ability that responds is through after the reaction in the plasma reaction level, flow into again in the order of reaction, it mixes with the warmed-up cooling air that comes in the annular gap there, and being cooled to about 1500 ℃, this temperature is enough to make the stable combustible H that constitutes by the plasma chemistry gasification in the plasma reaction level
2, CO is oxidized to CO
2And H
2O.In order to achieve the above object, reactor of the present invention is provided with the district of a plurality of intercommunications, especially will directly couple together as the annular gap of plasma reaction level cooling zone and order of reaction again, such structure can repeatedly be utilized the air that enters through inlet branch, both with it as cooling agent, again with it as warmed-up oxidant, do not carry out so oxidizing process can have difficultly.In order of reaction again, stable combustible there is the oxidation of control, at this moment because heat release will make this district carry out water-cooled by cooling-water duct.
Product CO
2, H
2O steam, HCl discharge through gas vent.
Since the pipe that at one end can fix loosely have by tensioner ring and and pipe between leave the possibility that the spacing pin that is installed with gap freely expands to the space, although therefore on pipe, receive the temperature load of very big thermic load (to 2000 ℃) and alternation, any thermal stress and mechanical stress can not appear, therefore the working life that has prolonged reactor yet.
In addition, no longer there is sealing problem by reactor of the present invention, because for the plasma reaction level, the transition position between plasmatron flange and pipe, in the annular gap, the bigger pressure loss is arranged, therefore no longer need sealing in principle because of flow velocity is higher.
All the time there is a small gangs of cooling air stream to flow into the plasma reaction district from the annular gap, this does not have bad effect for the plasma reaction in the plasma reaction level, but Toxic is gone in across and into the annular gap from the plasma reaction level.Owing to this reason does not need to compress pipe, thereby avoid producing thermal stress and mechanical stress.
Remove malicious device instantiation explanation the present invention by means of one below.
This device is to 7 meters of flow average out to
3/ hour and composition (percentage by volume) be 90%N
2
The hydrocarbon of 3% chlorine
(＞300 perchloride)
4%BCl
3
2%Cl
3
1%HCl
Waste gas stream thoroughly remove poison, and the gas that they is converted into environmental sound and human body and biosphere not have influence.The waste gas flow path is to spraying into plasma chemical reactor, the water vapor plasma bundle is arranged in the reactor, this plasma bundle is provided by a plasmatron, its parameter is:1.5 kilograms/hour of steam vapour amounts, 6.6 kilowatts of plasma beam power, 2900 ℃ of of of of the mean temperatures of plasma beam material, the percent by volume of plasma beam chemical equilibrium compositions under the material mean temperature is:H2O 50.00
H
216.00
H 10.00
OH 12.36
O 4.7
O
25.5
Waste gas and water vapor plasma bundle are after the blending of mixed zone, the mean temperature of material at this moment is about 2000 ℃, whole chemical reactions (waiting stripped chemistry to remove halogen and corresponding gas), with plasma reactor that plasmatron 2 is connected in primary plasma order of reaction 14 in carry out.Through after the reaction time, in the secondary reaction level 15 of joining with it that this order of reaction is not held, sneak into 10 meters
3/ hour preheated air, and article on plasma body bundle and secondary reaction are carried out " quenching " (Abloeschen), the stable combustible H that the oxidation of with clearly defined objective ground generates in plasma reactor simultaneously thus
2And CO.When leaving order of reaction, throughput is about 17 meters again
3/ hour, air-flow is by HCl, N
2, Co
2, steam and O
2Form.The temperature of air-flow is about 1500 ℃.This strand air-flow sprays it with 500 liters/hour sodium hydroxide solutions in being located at a pre-absorption device of back, therefore has two-phase in same flowing.The consumption of sodium hydroxide solution is according to making air-flow be cooled to about 100 ℃ and do not make alkali lye produce evaporation to determine.Absorbed a part of HCl simultaneously and come out from the pre-absorption device, to alleviate the burden of the packed column that is located at the back, gas phase and liquid sodium hydroxide solution are separately discharged, and the sodium hydroxide solution input is located in the packed column of back, and gas phase is sent into the packed column bottom.
After air-flow washs in packed column only by N
2, O
2, CO
2Form with steam, and can harmlessly enter surrounding environment through gas passage.But also the stable combustible that can not adopt again the order of reaction burning-off to come out from the plasma reaction level replaces and carries out with clearly defined objective quenching.As cooling lentamente can generate hydrocarbon, do like this and cause producing the halogen hydrogen compound, can further utilize them.Therefore can reduce the oxygen content of cooling agent.
Accompanying drawing is expressed the additional exotic material concentric tube that has, and as the reactor basic structure of preferred plan.
Reactor links to each other with plasmatron 2 through plasmatron flange 1.The radial passage 3 of input waste material, axial beam-plasma passage 4 and cooling-water duct 5 as mixing chamber are arranged in plasmatron flange 1.Deviate from plasmatron 2 those sides on plasmatron flange 1, be equipped with vertically and extend, innerly be the tensioner ring 6 of taper, the pipe of being made by carborundum 7 is not placed on the plasmatron flange 1 regularly round tensioner ring, and locatees by cone expansion ring 6.The pipe 7 of upward opening is surrounded coaxially by plasma reactor shell 8, is being close to plasmatron flange 1 place on the shell and is establishing cooling air inlet branch 9.It between pipe 7 and the shell 8 spacing pin 11 is arranged, even also can locate pipe 7 at an upper portion thereof under operating temperature unstressedly.Therefore, between pipe 7 and shell 8, formed a cooling air annular gap 10.Connecting the bilayer sleeve 12 that has cooling-water duct 13 and corresponding cooling water inlet branch 16 and be located at the gas vent 17 of central authorities by flange 18 on shell 8 extension vertically.Pipe 7 terminates in the order of reaction again 15 of flange 18 back.Therefore plasma reactor has been divided into the zone 4,10,14,15 that interconnects.
When for example in the groove of cone expansion ring 6, inserting another axial length made with carborundum and diameter all than the little pipe 19 of pipe 7, just one that has obtained article on plasma precursor reactant device is replenished, therefore constituted the less additional mixer 20 of a diameter of water vapor plasma and waste material, at an upper portion thereof, between mixer 20 and plasma reaction level 14 during transition, owing to the seamed edge of the carborundum tube 19 that exists has formed strong turbulent flow.
Reactor of the present invention can pressed under the condition of method of the present invention, by realizing the gentle wall temperature of high core, even destroy high stability refuse fully; , and utilize cooling-air to separate out plasma beam and enclose all environment guaranteeing the most reasonable energy that utilizes with the working method of single-stage; Warmed-up cooling-air also is used as oxidant simultaneously. Reactor thermal efficiency height although reactor material stands big thermic load, still has very long working life. In addition, it also can be used for other plasma pyrolysis process.
The present invention also has other series of advantages except the major advantage with thorough annihilating toxical waste:
-use cheap steam as plasma gas,
-cancelled collection, intermediate storage and the conveying of hazardous waste,
The construction in-cancellation dedicated storage storehouse,
-in the method, do not generate new noxious material,
-destroyed whole toxic compounds and this class inorganic nature in refuse,
-the present invention is suitable in the microelectronics industry high request to white area and gray area,
-this method is equally applicable to the destruction of liquid towards, solid-state, ointment shape and off-gas, thus can extensively adopt,
-this method and this reactor all also can be used for the toxic waste of less stable, and they are lower than in temperature under 1300 ℃ the condition decomposes in other course of reaction.
Claims (7)
1, annihilating toxical waste, the method for the toxic waste of the hydrocarbon of especially chloride or fluorine, it is characterized by: it is intrafascicular that toxic waste is directly sent into water vapor plasma; In a back to back plasma reaction level (14), realize 10
-3The minimum reaction time of second; Plasma beam is being not less than 10 in the order of reaction again (15) in plasma reaction level exit
-2Second reaction time in, and consider and make full use of residual enthalpy and make temperature be no more than the effect of oxidated medium under 1500 ℃ the condition; After the oxidation product gas that is produced is carried out known alkali cleaning.
2, in accordance with the method for claim 1, it is characterized by: gaseous state, liquid state and ointment shape refuse are directly sent into the water vapor plasma bundle, and solid waste is worn into the granularity less than 300 microns earlier, relend that to help carrier gas to send into water vapor plasma intrafascicular.
3, in accordance with the method for claim 1, it is characterized by: oxide isolation is a kind of gaseous mixture that contains free oxygen.
4, in accordance with the method for claim 3, it is characterized by: oxide isolation is an air.
5, in accordance with the method for claim 1, it is characterized by: with alkali lye prewashing and be cooled to be lower than 100 ℃, then washing once more in packed column is to be cooled to ambient temperature in a pre-absorption device for product gas.
6, plasma chemical reactor, be used in particular for annihilating toxical waste, it links to each other with plasmatron (2) by plasmatron flange (1), be useful on the radial passage (3) of refuse being imported central plasma beam passage (4) on the plasmatron flange (1), it is characterized by: on plasmatron flange (1), connecting a cone expansion ring (6) that is arranged in plasma reactor, pine is being overlapped a pipe made from exotic material (7) on the tensioner ring, separated by a distance and coaxially round the pipe (7) a cylindrical plasma reactor shell (8) is housed, shell (8) is provided with the spacing pin (11) to pipe (7), and locate to be provided with inlet branch (9) near plasmatron flange (1) at it, shell (8) is shorter than pipe (7), on shell (8), connecting its internal diameter cylindrical bilayer sleeve (12) identical, cooling agent inlet branch (16) is being housed on the bilayer sleeve (12) with shell (8) internal diameter.
7, according to the described plasma chemical reactor of claim 6, it is characterized by: in pipe (7), another pipe made from exotic material (19) is housed coaxially, it is rigidly fixed on the cone expansion ring (6), its diameter is less than pipe (7), and axial length has only half of pipe (7) axial length at most.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD31883288A DD298459A7 (en) | 1988-08-11 | 1988-08-11 | PLASMACHEMIC REACTOR, IN PARTICULAR FOR DESTROYING TOXIC PRODUCTS |
| DDWPF23G/318832-4ALT | 1988-08-11 | ||
| DD31883388A DD299915A7 (en) | 1988-08-11 | 1988-08-11 | METHOD FOR THE TOTAL DESTRUCTION OF TOXIC ABPRODUCTS |
| DEWPH05H/318832 | 1988-08-11 | ||
| DEWPF23G/318833 | 1988-08-11 | ||
| DDWPF23G/318833-2 | 1988-08-11 | ||
| DDWPH05H/3188832-4NEU | 1988-08-11 | ||
| DEWPF23G/318832 | 1988-08-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040148A true CN1040148A (en) | 1990-03-07 |
| CN1023192C CN1023192C (en) | 1993-12-22 |
Family
ID=25748223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89105527.4A Expired - Fee Related CN1023192C (en) | 1988-08-11 | 1989-08-10 | Method for annihilating toxical waste and plasma chemical reactor |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5108718A (en) |
| JP (1) | JPH02107387A (en) |
| CN (1) | CN1023192C (en) |
| AT (1) | AT402338B (en) |
| DE (1) | DE3922383C2 (en) |
| FI (1) | FI893774A (en) |
| FR (1) | FR2635371B1 (en) |
| GB (1) | GB2222600B (en) |
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-
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- 1989-07-07 DE DE3922383A patent/DE3922383C2/en not_active Expired - Fee Related
- 1989-07-07 AT AT0166189A patent/AT402338B/en not_active IP Right Cessation
- 1989-07-14 US US07/380,169 patent/US5108718A/en not_active Expired - Fee Related
- 1989-08-01 GB GB8917589A patent/GB2222600B/en not_active Expired - Fee Related
- 1989-08-10 CN CN89105527.4A patent/CN1023192C/en not_active Expired - Fee Related
- 1989-08-10 FI FI893774A patent/FI893774A/en not_active Application Discontinuation
- 1989-08-11 JP JP1207084A patent/JPH02107387A/en active Granted
- 1989-08-11 FR FR8910820A patent/FR2635371B1/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036635C (en) * | 1992-03-04 | 1997-12-10 | 联邦科学和工业研究组织 | treatment of materials |
| US5866753A (en) * | 1992-03-04 | 1999-02-02 | Commonwealth Scientific | Material processing |
| CN100469467C (en) * | 2003-12-12 | 2009-03-18 | 中国科学院力学研究所 | Equipment and method of combined plasma arc and electric heat for cracking organic waste |
| CN102183029A (en) * | 2011-03-07 | 2011-09-14 | 北京赛必达生物技术有限公司 | Tail gas treatment furnace of annular plasma torch |
| CN106512883A (en) * | 2011-03-18 | 2017-03-22 | 加拿大派罗杰尼斯有限公司 | Steam plasma arc hydrolysis of ozone depleting substances |
| CN105864801A (en) * | 2015-02-09 | 2016-08-17 | 日本派欧尼株式会社 | Waste gas combustion type purifying device |
| CN112619334A (en) * | 2020-10-22 | 2021-04-09 | 无锡英普朗科技有限公司 | High-temperature plasma reaction device |
Also Published As
| Publication number | Publication date |
|---|---|
| FI893774A (en) | 1990-02-12 |
| GB2222600B (en) | 1993-04-21 |
| JPH02107387A (en) | 1990-04-19 |
| CN1023192C (en) | 1993-12-22 |
| US5108718A (en) | 1992-04-28 |
| GB8917589D0 (en) | 1989-09-13 |
| JPH0585231B2 (en) | 1993-12-06 |
| DE3922383C2 (en) | 1994-06-09 |
| GB2222600A (en) | 1990-03-14 |
| DE3922383A1 (en) | 1990-02-15 |
| ATA166189A (en) | 1996-08-15 |
| FR2635371B1 (en) | 1994-04-29 |
| AT402338B (en) | 1997-04-25 |
| FI893774A0 (en) | 1989-08-10 |
| FR2635371A1 (en) | 1990-02-16 |
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